CN102965646A - Stable catalyst solution for electroless metallization - Google Patents

Stable catalyst solution for electroless metallization Download PDF

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Publication number
CN102965646A
CN102965646A CN2012103952144A CN201210395214A CN102965646A CN 102965646 A CN102965646 A CN 102965646A CN 2012103952144 A CN2012103952144 A CN 2012103952144A CN 201210395214 A CN201210395214 A CN 201210395214A CN 102965646 A CN102965646 A CN 102965646A
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metal
gallic acid
catalyzer
acid
substrate
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CN102965646B (en
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K·M·米鲁姆
D·E·克莱利
M·A·热兹尼克
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Rohm and Haas Electronic Materials LLC
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper

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  • General Chemical & Material Sciences (AREA)
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  • Dispersion Chemistry (AREA)
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Abstract

Catalysts include nanoparticles of catalytic metal and gallic acid or gallic acid derivatives or salts thereof. The catalysts are used in electroless metal plating. The catalysts are free of tin.

Description

The rugged catalyst of electroless plating
Technical field
The present invention relates to the stable aqueous catalyst solution for electroless plating.Further, the present invention relates to not carry out stable stably catalyzed agent solution for the stanniferous of electroless plating and by gallic acid, gallic acid derivative and salt thereof.
Background technology
The chemical plating metal sedimentation is the well-known method for the substrate surface depositing metal layers.The electroless plating of insulator surface need to be used catalyzer in advance.The most frequently used catalysis or activate the method for isolator such as the non-conductive part for the production of the thin plate substrate of printed circuit board (PCB), is to process substrate with the tin in the acid chloride medium/palladium colloid aqueous solution.The structure of colloid was widely studied.As a rule, colloid comprises the metallic palladium nuclear that is surrounded by the stabilizing layer of tin ion (II), and described tin ion is in fact as the SnCl that avoids the coalescent surface-stable group of colloid in the suspension 3 -The title complex shell.
In activation method, on tin/palladium colloid catalyst is adsorbed onto at the bottom of the insulator-base, as contain the substrate of epoxy or polyamine, with the activating chemical metal deposition.In theory, catalyzer is transferred to electronics on the metal ion from reductive agent in electroless plating tank as transfer transport path carrier.Although the performance of electroless plating is subjected to many factors, such as the interpolation component of coating solution, activation step is the speed of control electroless plating and the key of mechanism.
In recent years, along with sizes of electronic devices reduce and to the increase of performance requirement, the demand to the zero defect electronic circuit in electronic circuit assembling industry is increasing gradually.Although in decades commercially with the catalyzer of tin/palladium colloid as electroless plating, and provide acceptable service, along with the further raising to the electronics specification of quality, many drawbacks of such catalyzer also show especially out gradually.The stability of tin/palladium colloid is main Consideration.Aforesaid tin/palladium colloid is stablized with one deck tin ion (II), and its pair anion can stop the coalescent of palladium.Catalyzer is to air-sensitive, be oxidized to tin (IV) easily, and colloid can not keep its colloidal structure like this.The rising of temperature and the meeting of stirring further promote this oxidation in the electroless plating process.If the concentration of tin (II) is down to danger level, as close to zero, the metallic palladium particles size can become greatly, produce coalescent and deposit, thereby loses catalytic activity.Just increased thus the demand to more stable catalyzer.In addition, the expensive and price volalility of palladium also impels and seeks more cheap metal on the industry.
Paid the considerable novel improvement catalyzer that strives to find.Because the cost of palladium is high, much make great efforts to be devoted to develop the catalyzer that does not contain palladium, such as the colloidal silver catalyzer.The another one research direction then is to develop not stanniferous palladium catalyst, and this is because the tin of tin chloride cost height and oxidation needs independent accelerating step.In addition, increased extra step in whole chemical plating method, the material that uses in accelerating step often can peel off by the suprabasil catalyzer of plating, thereby stays undesirable dead zone in coating.This often occurs on the glass fabric substrates that is generally used for printed circuit board (PCB) production.Yet this not stanniferous catalyzer shows as active and the reliability deficiency when being used for the plating of through hole of printed circuit board (PCB) production.And, this catalyzer active can reduction gradually in storage normally, thus cause this catalyzer unstable, be unsuitable for commercial applications.
Studied another steady component for tin composite, such as Polyvinylpyrolidone (PVP) (PVP) and tree-shaped polymkeric substance.A plurality of research institutions disclose the nanoparticle by the PVP protection of stable and homogeneous in the literature.Reported other metallic colloid in the document, the silver/palladium and the copper/palladium that are replaced by base metal such as the part palladium; Yet, also do not have up to now commercial acceptable alternative tin/palladium colloid catalyst.Therefore, stable, reliable chemical plating catalyst is still had demand.
Summary of the invention
Method comprises: substrate a) is provided; B) aqueous catalyst solution is applied in the substrate, aqueous catalyst solution comprises the nanoparticle of one or more metals, and metal is selected from silver, gold, platinum, palladium, iridium, copper, aluminium, cobalt, nickel and iron, and one or more are selected from gallic acid, the compound of gallic acid derivative and salt thereof, catalyzer are not stanniferous; And c) use electroless plating tank that metallochemistry is deposited in the substrate.
This catalyzer can be used for metallochemistry is plated in the substrate that comprises insulating material and, its store and the electroless plating process in all can keep stablizing; Reason is, compares with the tin/palladium catalyst of routine, and this catalyzer is difficult for oxidation.This catalyzer is biodegradable, so just can not produce environmental hazard.Gallic acid, gallic acid derivative and salt thereof in conventional tin/palladium catalyst, have the function of stablizer such as tin chloride, but gallic acid, the environmental hazard when gallic acid derivative and salt thereof can not produce picture processing tin chloride.Gallic acid, gallic acid derivative and salt thereof also have the function of reductive agent when existing with the nano particle form, it also can be used as antioxidant with the extending catalyst life-span.Use gallic acid, the stable metal catalyst of gallic acid derivative and salt thereof need not that accelerating step can be carried out electroless plating and to substrate, or even the through-hole wall of printed circuit board (PCB) carries out metal-plated.
Description of drawings
Accompanying drawing 1 is the classification comparison diagram backlight of the stable catalyzer of 300ppm Ag/150ppm gallic acid and conventional tin/palladium catalyst; And
Accompanying drawing 2 is classification comparison diagrams backlight of the stable catalyzer of 400ppm Ag/200ppm gallic acid and conventional tin/palladium catalyst.
Embodiment
Except clearly showing in the literary composition, following have following implication: g=gram at the used abbreviation of specification sheets full text; The mg=milligram; The ml=milliliter; The L=liter; Cm=centimetre; M=rice; The mm=millimeter; μ m=micron; The nm=nanometer; Ppm=hundred is content very much; ℃=degree centigrade; Every liter of g/L=gram; The DI=deionization; The wt%=weight percentage; And T g=second-order transition temperature.
The present invention in full used term " printed circuit board (PCB) " and " printed-wiring board (PWB) " is used interchangeably.The term of this specification " plating " and " deposition " are used interchangeably.Unless specialize, all consumptions are weight percentages.Also by any way combination in all numerical ranges all are included in is as long as these numerical range total amounts are 100% in logic.
Aqueous catalyst solution comprises the nanoparticle of metal, and metal is selected from silver, gold, and platinum, palladium, iridium, copper, aluminium, cobalt, nickel and iron, and one or more are selected from gallic acid, the stable compound of gallic acid derivative and salt thereof.Preferably, metal is selected from silver, palladium and gold, and more preferably metal is selected from silver and palladium, and most preferred metal is selected from silver.Preferably, stable compound has general formula:
Wherein R be-H or-(CH 2) X-CH 3, x is the integer that is selected from 2-4, and R 1, R 2, R 3, R 4And R 5For-H or-OH, it can be identical or different, condition is at least one or R 1, R 2, R 3, R 4And R 5For-OH, preferred R is-H that more preferably, R is-H and R 2, R 3And R 4For-OH.Compound for example comprises gallic acid, resorcylic acid, and hydroxy-benzoic acid, 2,4,6-trihydroxybenzoic acid and gallic acid ester are such as the gallic acid propyl ester.Normally, salt is sodium salt or sylvite.Preferred compound is gallic acid.
Comprise the stable component of q.s in the aqueous catalyst solution so that required stability and metal-plated to be provided.Carry out a small amount of test and just can obtain the usage quantity that obtains in order to specific concrete stablizer or the stablizer mixture of rugged catalyst and metal-plated.Usually, the amount of one or more stable compounds in the aqueous catalyst solution is 50ppm to 1000ppm, preferred 100ppm to 500ppm.
Choose wantonly, except gallic acid or gallic acid derivative, also can contain one or more reductive agents so that metal ion is reduced into metal.Can use the known conventional reduction agent that metal ion can be reduced into metal.Described reductive agent includes but not limited to dimethyamine borane, sodium borohydride, and xitix, different-xitix, sodium hypophosphite, hydrazine hydrate, formic acid and formaldehyde.The amount of contained reductive agent can be reduced into metal with all metal ions basically.Described consumption normally conventional amount used, be that one of ordinary skill in the art are known.
Source metal comprises this area and known in the literature common metal salt brine solution, and it can provide the metal with catalytic activity.Can use the mixture of two or more catalytic metals.The salt that comprises the described metal of the amount that 100ppm to 2000ppm, preferred 300ppm to 1500ppm can be provided.Silver salt includes but not limited to Silver Nitrate, Silver monoacetate, Silver Trifluoroacetate, toluenesulphonic acids silver, silver trifluoromethanesulfonate, silver fluoride, silver suboxide, Sulfothiorine silver, potassium cyanide silver.Palladium salt includes but not limited to Palladous chloride, palladium, Repone K palladium, sodium-chlor palladium and Palladous nitrate.Gold salt includes but not limited to gold tricyanide, gold perchloride, gold tribromide, potassium auric chloride, potassium auric cyanide, gold sodium chloride and gold sodium cyanide.Platinum salt includes but not limited to platinum chloride and platinum sulfide.Iridium salt includes but not limited to tribromide iridium, Repone K iridium.Mantoquita includes but not limited to copper sulfate and cupric chloride.Nickel salt includes but not limited to nickelous chloride and single nickel salt.Cobalt salt includes but not limited to that acetic acid bores, cobalt chloride, and cobaltous bromide and sulfate of ammoniac bore.Aluminium salt includes but not limited to Tai-Ace S 150 and aluminum sodium sulfate.Molysite includes but not limited to ferrous ammonium citrate, Ferrox ammonium and ferrous ammonium sulphate.Normally, metal-salt is silver, palladium and gold.Preferably metal-salt is silver and palladium.More preferably metal-salt is silver.
Each component that forms aqueous catalyst solution can any sequential combination.Can use any suitable method Kaolinite Preparation of Catalyst aqueous solution of this area and known in the literature.The design parameter of component and consumption can be made change in diverse ways, in general, at first one or more stable compounds are dissolved in the enough water.The aqueous solution of one or more source metal is mixed to get uniform mixture by vigorous stirring and stabiliser solution.Choose wantonly, the aqueous solution that will contain again one or more reductive agents mixes with the phase of mixing of stablizer and metal-salt under vigorous stirring.Usual method step and solution at room temperature carry out; Yet the capable of regulating temperature is to help the reduction of solubilizing reaction component and promotion metal ion.Be not limited to theory, stablizer can apply or surround the part of metal or most of with stably catalyzed agent solution.The grain size scope of metal and stablizer is at least 1nm, generally is 1nm to 1000nm, perhaps 2nm to 500nm.Preferably the grain size scope is 2nm to 300nm, more preferably 2nm to 100nm and especially preferred 2nm to 10nm.
Can in acidity to weakly alkaline scope, before catalyzer is used for electroless plating, pH being down to below 7 of described synthetic catalyzer.One or more acid or its salt can be added in the catalyzer to obtain the pH less than 7, preferred 1-6.5, more preferably 2-6.Can use the mineral acid of q.s or organic acid or its salt to obtain the pH of required scope.Also can use mixture inorganic and organic acid and its salt.The embodiment of mineral acid comprises hydrochloric acid, sulfuric acid and nitric acid.Organic acid comprises list or poly carboxylic acid, such as dicarboxylic acid.The organic acid specific embodiment can be phenylformic acid, and xitix is different-xitix, oxysuccinic acid, toxilic acid, oxalic acid, acetic acid, citric acid and tartrate.
Catalyzer can be used for the multiple substrate of electroless plating.Such substrate includes but not limited to comprise such as glass, pottery, porcelain, resin, paper, the inorganic and organic radical bottom material of cloth and composition thereof.Clad and use the substrate of catalyzer metallizing without the clad material.
Substrate also comprises printed circuit board (PCB).Described printed circuit board (PCB) comprises clad and without clad, it has used thermosetting resin, and thermoplastic resin and composition thereof comprises fiber, such as the embodiment of glass fibre and aforesaid dipping.
Thermoplastic resin includes but not limited to Derlin, and acrylate is such as methyl acrylate, celluosic resin, such as ethyl acetate, cellulose propionate, cellulose acetate butyrate (cellulose acetate butyreate) and nitrocellulose, polyethers, nylon, polyethylene, polystyrene, styrene mixture, for example vinyl cyanide vinylbenzene and multipolymer and acrylonitrile-butadiene styrol copolymer, polycarbonate, polychlorotrifluoroethylene, with vinyl polymer and multipolymer, vinyl-acetic ester for example, vinyl alcohol, the vinyl butyral, vinylchlorid, vinylchlorid-acetic ester multipolymer, vinylidene chloride and vinyl formal (formal).
Thermosetting resin includes but not limited to phthalic acid propenyl ester, furans, carbamide, P-F and phenol-furfural multipolymer, its use separately or with following mixed with resin: butadiene acrylonitrile copolymer or acrylonitrile-butadiene-styrene copolymer, polyacrylic ester, silicones, urea formaldehyde, Resins, epoxy, allylic resin, glyceryl phthalate and polyester.
Porous material includes but not limited to paper, timber, and cloth and fiber, natural and synthon for example are such as cotton fibre and trevira.
Catalyzer can be used for the low and high T of plating gResin.Low T gResin has and is lower than 160 ℃ Tg, high T gResin has 160 ℃ and above T gResin.Common high T gResin has 160 ℃ to 280 ℃ T g, perhaps be 170 ℃ to 240 ℃.High T gFluoropolymer resin includes but not limited to tetrafluoroethylene (PTFE) and teflon mixture.Described mixture comprises, for example contains PTFE and the cyanate of polyphenylene oxide.Other classes comprise and have high T gThe fluoropolymer resin of resin, include but not limited to Resins, epoxy, such as difunctional or multi-functional epoxy resin, bismaleimides/triazine and Resins, epoxy (BT epoxy), epoxy/polyphenylene oxide resin, acronitrile-butadiene-styrene, polycarbonate (PC), polyphenylene oxide (PPO), polyphenylene oxide (PPE), polyphenylene sulfide (PPS), poly-sulphur sulfone (PS), polymeric amide, polyester is such as poly-terephthalic acid second diester (PET) and Polybutylene Terephthalate (PBT), polyetherketone (PEEK), liquid crystalline polymers, urethane, polyetherimide, epoxide and their mixture.
Catalyzer is used in metal refining on the wall of the through hole of printed circuit board (PCB) or through hole.Catalyzer can be used for producing level or the vertical processing of printed circuit board (PCB).
Aqueous catalyst solution can be used for the conventional chemical coating bath.Can expect, but this is with the metal of catalyzer for any electroless plating of electroless plating, normally, described metal is selected from copper, copper alloy, nickel or nickelalloy.More generally, metal is selected from copper and copper alloy, the most normally uses copper.Commercial available chemical copper coating bath is CIRCUPOSIT TM880 chemical copper coating baths (can be obtained by the Rohm And Haas Electronic Mater (Rohm and Haas Electronic Material) in Massachusetts, United States Marlborough city).
Normally, copper ion source includes but not limited to the soluble halide of copper, nitrate, acetate, the aqueous solution of other organic or inorganic hydrochlorate of vitriol and copper.Can use the mixture of one or more described mantoquitas to obtain cupric ion.Embodiment comprises copper sulfate, such as cupric sulfate pentahydrate, and cupric chloride, cupric nitrate, copper hydroxide and thionamic acid copper.Can in composition, use the mantoquita of convention amount.Usually the copper ion concentration scope in the composition is 0.5g/L to 30g/L.
In the electroless plating composition, also can comprise one or more alloyed metals.Described alloyed metal includes but not limited to nickel and tin.The example of copper alloy comprises copper/nickel and copper/tin.Normally, copper alloy is copper/nickel.
The nickel ion source of nickel and nickelalloy electroless plating tank can comprise one or more conventional nickel salt aqueous solutions.Nickel ion source includes but not limited to single nickel salt and nickel halogenide.The nickel ion source that also can comprise convention amount in the electroless plating alloy composite.Normally the amount of nickel ion is 0.5g/L to 10g/L.
The method steps that is used for base metal can be dependent on and is deposited the surface is metal or isolator and change.Concrete step and step order can change in diverse ways.Utilized the conventional steps that can adopt the electroless plating substrate in the method for catalyzer; But the stable metal catalyst aqueous solution of gallic acid and gallic acid then is different from many traditional chemical electroplating methods, does not need accelerating step.Correspondingly, preferably when using catalyzer without accelerating step.Normally, use the metal coating bath after catalyzer being applied to the substrate surface of chemical plating metal.The electroless plating parameter is conventional such as temperature and time.Can use conventional substrate preparation method, such as cleaning or the degreasing of substrate surface, roughening or the little-roughening on surface, etching or the little-etching on surface, swelling is used, through hole decontamination and various rinsing and antirust processing.Described method and preparation all are disclosed in the known in the art and file.
Normally, when the substrate of metal-plated is the surface of insulating material such as printed circuit board (PCB) or the wall of through hole, described plate water clean and rinsing and antirust after, through-hole wall is carried out decontamination processes.Normally, prepare with swelling at first or softening Surface Insulation or through hole decontamination.
Can use any traditional swelling.Concrete type can change according to the type of insulating material.The example of isolator as mentioned above.Can carry out small test to determine that swelling is applicable to special insulating material.The T of common insulating material gDetermined the type of used swelling.Swelling include but not limited to glycol ether and with the Acetic Ester of its combination.Can use convention amount glycol ether and with the Acetic Ester of its combination.Conventional available swelling example is CIRCUPOSIT TMConditioning agent 3302, CIRCUPOSIT TMHole Prep3303 and CIRCUPOSIT TMHole Prep4120 (can be obtained by Rohm And Haas Electronic Mater).
Choose wantonly, substrate and through hole water clean.Then make used additives.Can use conventional auxiliary agent.Described auxiliary agent comprises sulfuric acid, chromic acid, alkaline permanganate or plasma etching.Normally use alkalinity potassium permanganate as auxiliary agent.The example of the auxiliary agent that commerce is available is CIRCUPOSIT TMAuxiliary agent 4130 and CIRCUPOSIT TMMLB auxiliary agent 3308 (can be obtained by Rohm And Haas Electronic Mater).
Choose wantonly, water cleans substrate and through hole again.Then use in the neutralizing agent and the residue of auxiliary agent.Can use conventional neutralizing agent.Normally, neutralizing agent is the alkaline aqueous solution that contains one or more amine or 3wt% superoxide and 3wt% sulphuric acid soln.The example of the neutralizing agent that commerce is available is CIRCUPOSIT TMMLB neutralizing agent 216-5.Choose wantonly, dry after substrate and through hole water clean.
After swelling and the decontamination, use acidity or alkalescence to regulate.Available conventional conditioning agent.Described conditioning agent comprises one or more cats products, nonionogenic tenside, complexing agent and pH adjusting agent or buffer reagent.The example of the acid regulator that commerce is available is CIRCUPOSIT TMConditioning agent 3320 and CIRCUPOSIT TMConditioning agent 3327 (can be obtained by Rohm And Haas Electronic Mater).Suitable alkali conditioning agent includes but not limited to contain the basic surface promoting agent aqueous solution of one or more quaternary amines and polyamine.The example of the basic surface promoting agent that commerce is available is CIRCUPOSIT TMAuxiliary agent conditioning agent 231,3325,813 and 860.Choose wantonly, water cleans substrate and through hole.
Carry out little-etching after regulating.Can use conventional little-etch composition.Design little-be etched with in the metallic surface of exposing metal (for example, internal layer and surface etching) absorption of little-roughening to promote subsequently electroless plating and electroless plating afterwards be provided.Little-etching includes but not limited to the Sodium Persulfate of 60g/L to 120g/L or the mixture of the single persulfuric acid sodium oxide of oxidation or potassium and sulfuric acid (2%), or general sulfuric acid/hydrogen peroxide.Commercial available little-example of etch composition is CIRCUPOSIT TMMicroetch3330 and PREPOSIT TM748.Choose wantonly, water cleans substrate.
Then preimpregnation is carried out in little-etching substrate and through hole.The example of preimpregnation comprises 2% to 5% hydrochloric acid soln or the acidic solution of 25g/L to 75g/L sodium-chlor.Commercial available preimpregnation is CATAPREP TM404 (can be obtained by Rohm And Haas Electronic Mater).
Then will be used for substrate and through hole with gallic acid or gallic acid derivative or the stable catalyzer of its salt.Processed 1-10 minute with the catalyzer perfusion, be generally 2-8 minute.Temperature range is room temperature to 80 ℃, or for example 30 ℃-60 ℃.Choose wantonly, using behind the catalyzer again, water cleans substrate and hole.
Then with electroless plating tank with metal such as copper, copper alloy, the plating substrate of nickel or nickelalloy and through-hole wall.Normally, copper is plated on the through-hole wall.Time and the temperature of plating are conventional.Normally, metal deposition is preferably carried out under 30 ℃-60 ℃ at 20 ℃-80 ℃.Substrate can be immersed in the electroless plating tank or with plating bath and be ejected in the substrate.Normally, deposition can be carried out 5 seconds to 30 minutes; Yet, can be according to the time of the thickness adjustment of metal in substrate plating.
Choose wantonly, metal is prevented the variable color processing.Can use the conventional colour cell of preapring for an unfavorable turn of events to divide.The example of anti-variable color is ANTI TARNISH TM7130 (can be obtained by Rohm And Haas Electronic Mater).Choose wantonly, clean then drying circuit plate of substrate.
Further processing can comprise that conventional photosensitive imaging processes and deposit metal in further in the substrate such as copper copper alloy, the chemical metal deposition of tin and tin alloy.
Can use catalyzer to carry out chemical plating metal in substrate, this substrate comprises that the substrate of insulating material and this catalyzer all can keep stable in storage and electroless plating process, and than the tin/palladium catalyst of routine, above-mentioned catalyzer is difficult for oxidation.Described catalyzer is biodegradable, so it can not bring environmental hazard.Such as tin chloride conventional tin/palladium catalyst, gallic acid, gallic acid derivative and salt thereof have the function of stablizer, but gallic acid, the environmental hazard that gallic acid derivative and salt thereof can not produce picture when processing tin chloride.Gallic acid, gallic acid derivative and salt thereof have when existing with the nano particle form reductive agent function, it also can be used as antioxidant with the extending catalyst life-span.Use gallic acid, the stable metal catalyst of gallic acid derivative and salt thereof need not that accelerating step can be carried out electroless plating and to substrate, and the through-hole wall of printed circuit board (PCB) carries out metal-plated.
Following embodiment only is intended to explain the present invention, scope of the present invention is not construed as limiting.
Embodiment 1
Two groups and every group six different thin plates with a plurality of through holes are: NP-175,370HR, TUC-752, SY-1141, SY-1000-2, and FR-408.NP-175 derives from Nanya.370HR and FR4-408 derive from Isola.TUC-752 derives from Taiwan United Technologies (Taiwan Union Technology), and SY-1141, and SY-1000-2 derives from great kindness (Shengyi).The T of thin plate gThe scope of value is 140 ℃ to 180 ℃.Each thin plate is 5cm * 12cm.The through hole of each thin plate is processed with following method:
1. the through hole CIRCUPOSIT of each thin plate TMMLB conditioning agent 211 carries out decontamination in 7 minutes under 78 ℃ processes;
2. then clean the through hole 4 minutes of each thin plate with flowing water;
3. use CIRCUPOSIT TMMLB auxiliary agent 213 potassium permanganate solutions are 13,78 ℃ of lower processing through holes 10 minutes at pH;
4. then cleaned through hole 4 minutes with flowing water;
5. use CIRCUPOSIT TMMLB neutralizing agent 216-5 solution was processed through holes 5 minutes under 46 ℃;
6. then clean the through hole 4 minutes of each thin plate with flowing water;
7. then containing 3%CIRCUPOSIT TMProcessed through hole 5 minutes under 40 ℃ in the tank of the alkaline conditioner of conditioning agent 231;
8. then processed each thin plate through hole 4 minutes with flowing water;
9. then use PREPOST TM748 at room temperature processed through hole 2 minutes;
10. then process the through hole 4 minutes of each thin plate with flowing water;
11. then with the silver catalyst of 300ppm the through hole of six thin plates of 40 ℃ of lower perfusions 5 minutes, silver catalyst gallic acid stable Silver Nitrate under pH2.9 of coming free 150ppm wherein, the catalyst particle size scope is 7-10nm, the through hole CATAPREP of other six thin plates TM404 holes prepare agent at room temperature processed 1 minute, then processed 5 minutes under 40 ℃ with the conventional palladium that contains 100ppm palladium and excess chlorination tin/tin catalyst colloid;
12. then cleaned through hole 4 minutes with flowing water;
13. then thin plate is immersed in 38 ℃, pH and is 13 CIRCUPOSIT TMIn the 880 chemical copper coating baths, copper deposits 15 minutes at through-hole wall;
Immersed cold water 4 minutes 14. then copper is plated thin plate;
15. with dry each the copper plating thin plate of compressed gas; And
16. use following backlight method to detect the copper plating fraction of coverage of the through-hole wall of thin plate.
Every block of plate is cut into pieces to expose the copper plating wall of through hole.Cut into slices to determine the fraction of coverage of through-hole wall from 10 thick sides of section through-hole wall taking-up 1mm of each plate.Use European grading scale backlight.The 1mm section of taking from every block of plate is placed on the microscopically of conventional optional 50X x magnification.The copper deposition is that the amount of the light that observed by microscopically is determined.If do not observe light, section is deceived fully, and classification backlight is 5 grades, the completely copper fraction of coverage of its expression through-hole wall.Do not have dark region such as light by whole sections, then expression does not have seldom even copper to be deposited on the wall, and section is the O level.If section has some dark region, also have the light district, its rank is between 0 and 5.
Accompanying drawing 1 is classification distribution diagram backlight, and its expression has the performance backlight of the two kinds of catalyzer of each in six types of plating plates.Brilliant figure among the figure represents 95% fiducial interval of 10 through hole sections of every block of plate.The average backlight value that represents every part of ten measured through hole sections by the sea line at each diamond middle part.Except with the NP-175 plate of silver/gallic acid catalyst treatment, silver/gallic acid catalyzer has 4.5 or higher backlight value with in fact the same with conventional palladium/tin colloid catalyzer.Normally, 4.5 or higher backlight value represent its be the plating industry in commercial acceptable catalyzer.
Embodiment 2
Except the gallic acid of the silver from Silver Nitrate that contains 400ppm, 200ppm and oxalic acid as the silver of pH adjusting agent/gallic acid catalyzer, repeat the preparation method of embodiment 1.Described pH is 2.7, and silver/gallic acid nanoparticle size range is 7-10nm.In addition, thin plate was processed 7 minutes under 45 ℃ in catalyzer and was plated 20 minutes under 40 ℃.Before carrying out the catalyzer step and afterwards, replace flowing water to be used for cleaning thin plate with deionized water.Backlight the results are shown in the accompanying drawing 2.
In fact the result backlight of all silver/gallic acid catalyzer is more than 4.5, except the NP-175 thin plate has the value identical with embodiment 1.On the contrary, the backlight value major part of conventional palladium/tin colloid catalyzer is near 4.5, and the FR-408 thin plate is near 4.3, and this is lower than acceptable scope.On the whole, silver/gallic acid catalyzer has better plating result than conventional catalyst.

Claims (6)

1. method comprises:
A) provide substrate;
B) aqueous catalyst solution is applied in the substrate, this aqueous catalyst solution contains one or more and is selected from silver, gold, platinum, palladium, iridium, copper, aluminium, cobalt, the metallic nano-particle of nickel and iron, and one or more are selected from gallic acid, the stable compound of gallic acid derivative and salt thereof, described aqueous catalyst solution is not stanniferous; And;
C) with electroless plating tank metallochemistry is deposited in the substrate.
2. according to claim 1 method, wherein metal is selected from silver and palladium.
3. according to claim 1 method, wherein stable compound is selected from gallic acid, resorcylic acid, hydroxy-benzoic acid, 2,4,6-trihydroxybenzoic acid and gallic acid ester.
4. according to claim 1 method, wherein the electroless plating metal is copper, copper alloy, nickel or nickelalloy.
5. according to claim 1 method, wherein the diameter of nanoparticle is at least 1nm.
6. according to claim 1 method, wherein the consumption of one or more stable compounds is 50ppm to 1000ppm.
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